WO2015093524A1 - Polyester resin - Google Patents

Polyester resin Download PDF

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Publication number
WO2015093524A1
WO2015093524A1 PCT/JP2014/083396 JP2014083396W WO2015093524A1 WO 2015093524 A1 WO2015093524 A1 WO 2015093524A1 JP 2014083396 W JP2014083396 W JP 2014083396W WO 2015093524 A1 WO2015093524 A1 WO 2015093524A1
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WO
WIPO (PCT)
Prior art keywords
polyester resin
acid
polyester
reduced viscosity
thermal oxidation
Prior art date
Application number
PCT/JP2014/083396
Other languages
French (fr)
Japanese (ja)
Inventor
卓也 下拂
小林　幸治
Original Assignee
東洋紡株式会社
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=53402869&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2015093524(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by 東洋紡株式会社 filed Critical 東洋紡株式会社
Priority to EP14870679.9A priority Critical patent/EP3085723B1/en
Priority to ES14870679T priority patent/ES2907552T3/en
Priority to CN201480069403.XA priority patent/CN105849152B/en
Priority to JP2015511128A priority patent/JP5928655B2/en
Priority to DK14870679.9T priority patent/DK3085723T3/en
Priority to US15/104,852 priority patent/US9850342B2/en
Priority to KR1020167019004A priority patent/KR102218228B1/en
Publication of WO2015093524A1 publication Critical patent/WO2015093524A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/826—Metals not provided for in groups C08G63/83 - C08G63/86
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/87—Non-metals or inter-compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/049—Protective back sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a polyester resin excellent in long-term heat resistance and moldability, and a film, sheet, and injection molded article using the same.
  • the polyester resin excellent in heat resistance suitable for outdoor uses such as a solar cell backside sealing sheet, and a film, a sheet
  • polyester resin gradually decreases due to degradation and degradation of the polyester resin.
  • solar cell members and electrical insulation members are kept under high temperature and high humidity for a long period of time, how to suppress degradation and degradation of polyester resins used and films, sheets, and injection molded articles using the same. This is an important issue.
  • the degradation degradation of the polyester resin under high temperature and high humidity can be considered by dividing into thermal degradation and hydrolysis.
  • hydrolysis with water or water vapor is considered to proceed by the following reaction.
  • the nucleophilic attack on the ester bond of the water molecule causes the polymer chain to break up due to the hydrolysis reaction of the ester bond, thereby forming a carboxyl end and a hydroxyl end, and then the generated end hydroxyl group causes back-biting.
  • Polymer chain degradation continues.
  • the terminal carboxyl group plays a catalytic role in the hydrolysis reaction of the polymer, and the hydrolysis is accelerated as the amount of the terminal carboxyl group increases.
  • polyester resins having a small amount of terminal carboxyl groups have been proposed in order to suppress decomposition by heat, water, and water vapor (see, for example, Patent Documents 1 and 2). Although the amount of terminal carboxyl groups was certainly reduced by such a technique, long-term decomposition suppression was insufficient by itself.
  • One reason for this is that the molding temperature increases due to the high melting point of the polyester resin. That is, even if the hydrolysis rate is reduced by blocking the end of the polyester resin, a new carboxyl group is generated by the molecular chain being cut by the heat during molding. It cannot be suppressed.
  • an invention was made to improve heat resistance by using a titanium compound and a phosphorus compound in combination (for example, see Patent Document 3). If this method is used, a certain improvement in the heat resistance of the polymer is certainly observed, but the decomposition reaction is also promoted due to the high polymerization activity of the titanium compound, so the level is not necessarily sufficient. . Furthermore, when a phosphorus compound is added in a certain amount or more, the polymerization activity of the titanium compound is lowered, and the target polymerization degree is not reached, the polymerization time is remarkably increased, and there is a problem that productivity is deteriorated. It has not yet achieved both polymerization activity and sufficient heat resistance.
  • the present invention has been made against the background of the problems of the prior art. That is, the object of the present invention is to enable molding at a low temperature, suppress the formation of carboxyl groups by thermal decomposition, and further reduce the addition amount of a metal compound as a catalyst as much as possible while maintaining high polymerization activity. It is to obtain excellent long-term heat resistance.
  • the present inventor senses that the residual metal element of the polyester affects thermal degradation and hydrolysis, and makes the amount of the residual metal element extremely low.
  • the present invention has found the effect of exhibiting excellent long-term heat resistance for outdoor use such as solar cell back surface sealing, and has led to the present invention. That is, the configuration of the present invention is as follows.
  • a polyester resin comprising a dicarboxylic acid component and a glycol component, comprising 10 mol% or more of furandicarboxylic acid as a dicarboxylic acid component and satisfying the following requirements (1) to (3): (1) The total metal element content is 150 ppm or less with respect to the mass of the polyester resin. (2) The phosphorus element content is 100 ppm or less with respect to the mass of the polyester resin.
  • TOD ⁇ reduced viscosity is 0.030 dl / g or less
  • TOD ⁇ reduced viscosity (reduced viscosity before thermal oxidation test)
  • ⁇ reduced viscosity after thermal oxidation test
  • the thermal oxidation test is a polyester resin that has been melted for 2 minutes at a temperature of the melting point of the polyester resin + 30 ° C. in air and then given a thermal history under the load (100 kgf / cm 2 ) for 1 minute at the same temperature
  • the polyester resin of the present invention is excellent in long-term thermal stability. Therefore, it is useful as a constituent member for solar cell applications used outdoors.
  • the polyester resin of the present invention contains a catalyst (metal element) in polyester and is a kind of composition, but the catalyst is expressed as “resin” because the amount of the catalyst is small.
  • the polyester resin of the present invention is characterized in that the total metal element content is 150 ppm or less with respect to the mass of the polyester resin. When a lot of metals are contained in the polyester, the thermal decomposition reaction of the polyester is accelerated at a high temperature, which may cause thermal degradation of the polyester. Therefore, in the present invention, the content of the metal element is set to 150 ppm or less from the viewpoint of maintaining the long-term thermal stability of the polyester resin.
  • the content of the metal element is preferably 100 ppm or less, more preferably 80 ppm or less, and further preferably 50 ppm or less. From the viewpoint of reducing the thermal deterioration of the polyester resin, the content of the metal element is preferably small. However, in order to promote the polymerization reaction during the production of the polyester, a transition metal or typical metal element is used as a catalyst within the concentration range. It is desirable to add. Therefore, the lower limit of the content of the metal element is preferably 1 ppm or more, more preferably 5 ppm or more, and further preferably 10 ppm or more. From the viewpoint of polyester productivity, it is desirable to select an appropriate catalyst type as described later in order to achieve sufficient catalytic activity while being within the above-mentioned content range.
  • the polyester resin of the present invention is mainly composed of a dicarboxylic acid component and a glycol component, and is obtained by copolymerizing three or more functional components as necessary.
  • a furan carboxylic acid component is copolymerized. While the furancarboxylic acid component has an aromatic ring structure, it has the effect of lowering the melting point of the resin by copolymerization, compared with terephthalic acid, which is often used as a raw material for polyester resins.
  • the molding temperature it is necessary to set the molding temperature to be equal to or higher than the melting point of the resin, but since the molding temperature can be set low by copolymerization of flange carboxylic acid, the formation of carboxyl groups due to thermal decomposition is suppressed, which is good. Long-term thermal stability can be obtained.
  • the three-dimensional structure of the polymer chain, etc., 2,5-furandicarboxylic acid is particularly preferable among the isomers.
  • the copolymerization ratio of furandicarboxylic acid used in the polyester resin of the present invention is required to be 10 mol% or more, preferably 15 mol% or more, more preferably 20 mol% or more with respect to the total dicarboxylic acid component. More preferably, it is particularly preferably 50 mol% or more, and may be 100 mol%. If it is less than 10 mol%, there is almost no effect of lowering the melting point, which is not preferable.
  • the dicarboxylic acid component other than furandicarboxylic acid used in the polyester resin of the present invention is not particularly limited, and is terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, 4,4′-dicarboxybiphenyl, 5-sodium sulfoisophthalate.
  • Aromatic dicarboxylic acids such as acids, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 2,5-norbornenedicarboxylic acid, tetrahydrophthalic acid, etc.
  • aliphatic dicarboxylic acids when an aliphatic dicarboxylic acid component is used, it is preferable to use an aromatic dicarboxylic acid because the melting point is further lowered and the heat resistance may be significantly lowered.
  • terephthalic acid and 2,6-naphthalenedicarboxylic acid are more preferable from the viewpoint of versatility and heat resistance.
  • one type or two or more types can be copolymerized.
  • the glycol component used in the polyester resin of the present invention is not particularly limited, but ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, , 4-butanediol, 2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, 1,10 -Aliphatic glycols such as decanediol, dimethylol tricyclodecane, diethylene glycol, triethylene glycol, bisphenol A, bisphenol S, bisphenol C, bisphenol Z, bisphenol AP, ethylene oxide adducts or propylene oxide of 4,4'-biphenol Adduct, 1,2-si B hexane dimethanol, 1,3-cyclohexane dimethanol, an alicyclic glycol such as 1,
  • the polyester resin of the present invention can be copolymerized with a trifunctional or higher functional carboxylic acid or a trifunctional or higher functional alcohol component as necessary in order to enhance the functionality such as mechanical strength.
  • the copolymerization ratio of the tri- or higher functional monomer is suitably about 0.2 to 5 mol% with respect to 100 mol% of all dicarboxylic acid components or 100 mol% of all glycol components. If the copolymerization ratio of the trifunctional or higher monomer is too low, the effect of copolymerization is not exhibited, and if the copolymerization ratio is too high, gelation may be a problem.
  • Tri- or higher functional carboxylic acids include trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid, trimesic acid and other aromatic carboxylic acids, 1, 2, Examples include aliphatic carboxylic acids such as 3,4-butanetetracarboxylic acid.
  • Examples of the tri- or higher functional alcohol component include glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, ⁇ -methylglucose, mannitol, and sorbitol.
  • hydroxycarboxylic acids, lactones, monocarboxylic acids and monoalcohols may be used as copolymerization components in the polyester resin of the present invention.
  • the copolymerization ratio of these copolymerization components is suitably about 5 mol% or less with respect to 100 mol% of all dicarboxylic acid components or 100 mol% of all glycol components.
  • hydroxycarboxylic acids include p-hydroxybenzoic acid, m-hydroxybenzoic acid, o-hydroxybenzoic acid, lactic acid, glycolic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxyiso Examples include butyric acid, 2-hydroxy-2-methylbutyric acid, 2-hydroxyvaleric acid, 3-hydroxyvaleric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, 6-hydroxycaproic acid, and 10-hydroxystearic acid.
  • lactones include ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, and the like.
  • Examples of monocarboxylic acids include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, p-tert-butylbenzoic acid, cyclohexane acid, 4-hydroxyphenyl stearic acid.
  • Examples of the monoalcohol such as acid include octyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, 2-phenoxyethanol and the like.
  • Polyester resin polymerization methods include a transesterification method using a diester carboxylic acid component and a glycol component as starting materials, and a direct esterification method using a dicarboxylic acid component and a glycol component as starting materials.
  • a catalyst such as Zn, Ca, Mg, etc. is added at the time of transesterification in order to ensure productivity, so the concentration range may not be satisfied. Therefore, the direct esterification method is preferred as the polyester polymerization method in the present invention.
  • oligomer physical properties before polycondensation are important. Specifically, it is preferable to carry out esterification without a catalyst, add a catalyst after esterification, homogenize by stirring, and then enter the polycondensation step at a stage where the oligomer acid value is 100 eq / ton or more. When the oligomer acid value is 100 eq / ton or more, in addition to the catalytic activity of the metal, the proton of the oligomer acts as a polycondensation catalyst to ensure productivity.
  • the oligomer acid value is preferably 200 eq / ton or more, and more preferably 300 eq / ton or more. In terms of proton catalytic ability, the higher the oligomer acid value, the better. However, when the oligomer acid value exceeds 600 eq / ton, polymerization may not proceed due to poor esterification, and the molecular weight may not increase.
  • the polymerization catalyst is preferably not a heavy metal from the viewpoint of environmental burden, and more preferably an aluminum compound from the viewpoint of polymerization activity and polyester physical properties.
  • the aluminum compound a known aluminum compound can be used.
  • aluminum compounds include carboxylates such as aluminum formate, aluminum acetate, basic aluminum acetate, aluminum propionate, and aluminum oxalate; inorganic acid salts such as aluminum chloride, aluminum hydroxide, and aluminum hydroxide chloride; Aluminum methoxide, aluminum ethoxide, aluminum iso-propoxide, aluminum n-butoxide, aluminum t-butoxide and other aluminum alkoxides, aluminum acetylacetonate, aluminum acetylacetate, etc. Examples include organoaluminum compounds, partial hydrolysates thereof, and aluminum oxide.
  • carboxylates, inorganic acid salts and chelate compounds are preferred, and among these, aluminum acetate, basic aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetylacetonate are particularly preferred.
  • the polymerization activity of the aluminum compound alone is low, and in order to ensure productivity, it is necessary to add 150 ppm or more with respect to all constituent units of the carboxylic acid component such as polyester dicarboxylic acid or polyvalent carboxylic acid. Therefore, in order to control the total metal element content to 150 ppm or less with respect to the polyester, it is preferable to add a phosphorus compound as a promoter for the purpose of increasing the polymerization activity.
  • the concentration of the phosphorus compound to be used as the cocatalyst is preferably 100 ppm or less as the phosphorus element content with respect to the mass of the polyester resin.
  • the phosphorus compound may be incorporated into the main chain of the polyester in the polyester polymerization reaction, and the durability of the polyester may be reduced.
  • the phosphorus element content relative to the polyester is more preferably 95 ppm or less, and even more preferably 90 ppm or less.
  • the phosphorus element content is preferably 1 ppm or more and more preferably 3 ppm or more for the purpose of increasing the polymerization activity.
  • the kind and the addition amount of the preferable phosphorus compound which should be used in this invention are mentioned later, it displays as an addition amount with respect to all the structural units of a carboxylic acid component as the addition amount of a phosphorus compound in that case.
  • the phosphorus compound used as the co-catalyst is not particularly limited, but it is preferable to use one or more compounds selected from the group consisting of phosphonic acid compounds and phosphinic acid compounds because the effect of improving the catalytic activity is great.
  • the effect of improving the catalytic activity is particularly large and preferable.
  • the phosphorus compound which has a phenol part in the same molecule from the point of improving the thermal oxidation stability of polyester is especially preferable.
  • the polyester resin of the present invention is, as a phosphorus compound containing a phenol moiety used as a co-catalyst, specifically 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid ethyl, 3,5-di- methyl tert-butyl-4-hydroxybenzylphosphonate, isopropyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, phenyl 3,5-di-tert-4-butyl-4-hydroxybenzylphosphonate, 3, Octadecyl 5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, lithium [3,5-di-tert-butyl-4-hydroxybenzylphosphone Acid ethyl], sodium [3,5-di-tert-butyl-4-hydroxy Ethyl benzylphosphonate], sodium [3,5-di-
  • diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate commercially available as Irganox 1222 (manufactured by BASF)
  • calcium bis [3, commercially available as Irganox 1425 commercially available as Irganox 1425 (manufactured by BASF)
  • ethyl 5-di-tert-butyl-4-hydroxybenzylphosphonate particularly preferred is particularly preferred.
  • the polyester of the present invention can also use titanium as a catalyst. Even when titanium is used as a catalyst, productivity can be secured with a small amount of addition, but titanium has high catalytic activity, so thermal oxidation degradation of polyester tends to occur under heating, and long-term thermal stability cannot be obtained. There is. Therefore, in the present invention, it is preferable to use a catalyst species other than titanium as the polyester catalyst species.
  • the polyester resin of the present invention can be suitably obtained by using the above-mentioned catalyst species, the total metal element amount relative to the polyester resin can be made 150 ppm or less. Therefore, the polyester resin of the present invention is excellent in thermal oxidation stability and can exhibit long-term thermal stability.
  • the polyester resin of the present invention satisfies a TOD ⁇ reduced viscosity represented by the following formula, which is an index of thermal oxidation stability, of 0.030 dl / g or less.
  • the thermal oxidation test is a method of freeze-pulverizing a polyester resin sample that has been melted for 2 minutes at a temperature of the melting point of the polyester resin + 30 ° C. in air and then given a thermal history for 1 minute under the load (100 kgf / cm 2 ). Then, after making powder of 100 mesh or less and vacuum-drying at 70 ° C. for 12 hours and 1 Torr or less, 0.3 g of this was weighed, put into a glass test tube, and heated in air at a temperature of 180 ° C. for 60 minutes. It is a test to do.
  • the decomposition rate is not constant, and the decomposition proceeds at an accelerated rate as the TOD ⁇ reduced viscosity increases. If the TOD ⁇ reduced viscosity is 0.030 dl / g or less, it can be used outdoors, but preferably 0.025 dl / g or less, more preferably 0.020 dl / g or less, and the lower limit is 0. . A TOD ⁇ reduced viscosity of 0.020 dl / g or less is desirable because the progress of the decomposition rate is suppressed.
  • the phosphorus compound preferably has a phenol moiety. This is because the phosphorus compound containing a phenol moiety has an effect of suppressing polyester degradation that is decomposed by a radical mechanism under oxygen. In order to enhance this function, it is more preferable that the phenol moiety has a hindered phenol skeleton that is sterically and electronically stabilized and expresses more radical trapping ability.
  • the reduced viscosity of the polyester resin of the present invention is not particularly limited, but is preferably 0.1 to 2.0 dl / g. If it is less than 0.1 dl / g, the mechanical strength is remarkably lowered and it becomes practically difficult to use. If it exceeds 2.0 dl / g, the melt viscosity becomes high and the handling property becomes poor, and the polymerization time becomes long, which may adversely affect productivity. It is preferably 0.2 to 1.8 dl / g, more preferably 0.3 to 1.5 dl / g.
  • a terminal blocking agent such as a carbodiimide compound, an oxazoline compound, or an epoxy compound is blended at an arbitrary ratio in order to block a carboxyl group that is generated when decomposition degradation occurs at high temperature and high humidity. May be.
  • polyester resin of the present invention In order to make the polyester resin of the present invention higher performance, generally well known stabilizers, lubricants, mold release agents, plasticizers, flame retardants, flame retardant aids, ultraviolet absorbers, light stabilizers, Pigments, dyes, antistatic agents, conductivity-imparting agents, dispersants, compatibilizing agents, antibacterial agents, various fillers, and the like can be added alone or in combination of two or more.
  • the polyester resin of the present invention can be formed into a film, a sheet, an injection-molded body or the like by a known molding method.
  • TOD ⁇ reduced viscosity (reduced viscosity before thermal oxidation test) ⁇ (reduced viscosity after thermal oxidation test)
  • polyester resin composition The composition and composition ratio of the polyester resin were determined by 1 H-NMR measurement (proton nuclear magnetic resonance spectroscopy) at a resonance frequency of 400 MHz.
  • Antimony trioxide was dissolved in an ethylene glycol solution to obtain an ethylene glycol solution of 14 g / l antimony trioxide.
  • Germanium dioxide was dissolved in water to obtain an aqueous solution of 8 g / L germanium dioxide.
  • TMPA Trimethyl phosphoric acid
  • TBT Tetra-n-butoxytitanium
  • Cobalt acetate was dissolved in ethylene glycol to obtain 20 g / l of an ethylene glycol solution of cobalt acetate.
  • Example 1 A 2-liter stainless steel autoclave equipped with a stirrer was charged with 428.5 g (2.7 mol) of 2,5-furandicarboxylic acid and 219.5 g (3.5 mol) of ethylene glycol. An esterification reaction was performed for 150 minutes under a pressure of 25 MPa to obtain an oligomer mixture. Thereafter, the prepared ethylene glycol solution of Irganox 1222 and the ethylene glycol mixed solution of aluminum compound are added so as to have a predetermined residual amount, and the temperature of the reaction system is gradually lowered while raising the temperature to 250 ° C. over 60 minutes. The polyester polycondensation reaction was further performed for 60 minutes at 250 ° C. and 13.3 Pa at 13.3 Pa (0.1 Torr).
  • the resin under slight pressure is discharged into cold water in a strand form and rapidly cooled, then held in cold water for 20 seconds, and then cut to obtain a cylinder-shaped pellet having a length of about 3 mm and a diameter of about 2 mm. It was. The characteristics of this polyester pellet are shown in the table.
  • polyester resins Examples 2 to 4 were produced by changing the kinds of raw materials and the mixing ratio. The composition, amount of residual metal, and physical properties of the obtained resin are shown in the table. These satisfied the range defined in the present invention and showed good thermal oxidation stability.
  • Comparative Examples 1-6 According to the polymerization method of Example 1, polyester resin comparative examples 1 to 5 were produced by changing the kind of raw materials and the blending ratio. The composition, amount of residual metal, and physical properties of the obtained resin are shown in the table. Since Comparative Example 1 contains too much phosphorus compound, Comparative Examples 2 to 5 have too much residual metal, so the thermal oxidation stability is poor and the TOD ⁇ reduced viscosity is more than 0.030 dl / g. It can be seen that is an unsuitable resin.
  • the polyester resin of the present invention is excellent in long-term thermal stability. Therefore, it is useful as a component for solar cell applications used outdoors and has a great industrial utility value.

Abstract

The present invention provides a polyester resin which exhibits excellent long-term thermal stability and excellent moldability. The polyester resin comprises a dicarboxylic acid component and a glycol component, includes, as the dicarboxylic acid component, at least 10 mol% of a furan dicarboxylic acid, and satisfies conditions (1)-(3): (1) that the total metal content be not more than 150 ppm with respect to the mass of the polyester resin; (2) that the phosphorus content be not more than 100 ppm with respect to the mass of the polyester resin; and (3) that the TOD∆ reduced viscosity represented by the formula (TOD∆ reduced viscosity)=(reduced viscosity before thermal oxidation test)-(reduced viscosity after thermal oxidation test) be not more than 0.030 dl/g.

Description

ポリエステル樹脂Polyester resin
　本発明は、長期耐熱性及び成形性に優れたポリエステル樹脂及びこれを用いたフィルム、シート、射出成形体に関する。詳しくは、太陽電池裏面封止シート等の屋外用途に好適な耐熱性、耐候性に優れたポリエステル樹脂及びこれを用いたフィルム、シート、射出成形体に関する。 The present invention relates to a polyester resin excellent in long-term heat resistance and moldability, and a film, sheet, and injection molded article using the same. In detail, it is related with the polyester resin excellent in heat resistance suitable for outdoor uses, such as a solar cell backside sealing sheet, and a film, a sheet | seat, and an injection molding using this.
　一般にポリエステル樹脂の性能は、ポリエステル樹脂の分解劣化により徐々に低下する。特に太陽電池部材や電気絶縁部材等は長期間にわたり高温高湿下におかれることから、使用されるポリエステル樹脂及びこれを用いたフィルム、シート、射出成形体について、いかに分解劣化を抑制するかが重要な課題である。 Generally, the performance of polyester resin gradually decreases due to degradation and degradation of the polyester resin. In particular, since solar cell members and electrical insulation members are kept under high temperature and high humidity for a long period of time, how to suppress degradation and degradation of polyester resins used and films, sheets, and injection molded articles using the same. This is an important issue.
　高温高湿下におけるポリエステル樹脂の分解劣化は、熱による分解と加水分解に分けて考えることができる。 The degradation degradation of the polyester resin under high temperature and high humidity can be considered by dividing into thermal degradation and hydrolysis.
　まず熱によるポリエステル樹脂の分解は、次のような反応により進行すると考えられている。まず熱によりエステル結合が開裂してポリマー鎖が切断され、カルボキシル末端基とビニルエステル末端が生成する。次いでビニルエステル末端からさらに反応してアセトアルデヒドを脱離する。 First, it is thought that decomposition of the polyester resin by heat proceeds by the following reaction. First, the ester bond is cleaved by heat and the polymer chain is cleaved to generate a carboxyl terminal group and a vinyl ester terminal. Subsequently, acetaldehyde is eliminated by further reaction from the vinyl ester terminal.
　また、水や水蒸気による加水分解は、次のような反応により進行すると考えられている。まず水分子のエステル結合への求核攻撃によってエステル結合の加水分解反応によるポリマー鎖の分裂が起こり、カルボキシル基末端と水酸基末端が形成され、次いで生成された末端水酸基はバックバイティングを引き起こし、さらにポリマー鎖の分解が継続する。この反応において、末端カルボキシル基はポリマーの加水分解反応の触媒的な役割を担い、末端カルボキシル基量の増加に伴って加水分解が加速される。 In addition, hydrolysis with water or water vapor is considered to proceed by the following reaction. First, the nucleophilic attack on the ester bond of the water molecule causes the polymer chain to break up due to the hydrolysis reaction of the ester bond, thereby forming a carboxyl end and a hydroxyl end, and then the generated end hydroxyl group causes back-biting. Polymer chain degradation continues. In this reaction, the terminal carboxyl group plays a catalytic role in the hydrolysis reaction of the polymer, and the hydrolysis is accelerated as the amount of the terminal carboxyl group increases.
　かかる熱や水、水蒸気による分解を抑制すべく、末端カルボキシル基量の少ないポリエステル樹脂が数多く提案されている（例えば、特許文献１、２参照）。かかる手法により、確かに末端カルボキシル基量は低減されたものの、それだけでは長期の分解抑制が不十分であった。この理由の１つとして、ポリエステル樹脂の融点の高さに起因して、成形温度が高くなることが挙げられる。すなわち、ポリエステル樹脂の末端を封鎖することにより加水分解速度を低下したとしても、成形時の熱により分子鎖が切断することにより、新たにカルボキシル基が生成するため、結局、加水分解を完全には抑制できない。 Many polyester resins having a small amount of terminal carboxyl groups have been proposed in order to suppress decomposition by heat, water, and water vapor (see, for example, Patent Documents 1 and 2). Although the amount of terminal carboxyl groups was certainly reduced by such a technique, long-term decomposition suppression was insufficient by itself. One reason for this is that the molding temperature increases due to the high melting point of the polyester resin. That is, even if the hydrolysis rate is reduced by blocking the end of the polyester resin, a new carboxyl group is generated by the molecular chain being cut by the heat during molding. It cannot be suppressed.
　一方、かかる分解劣化の問題を解決すべく、チタン化合物とリン化合物を併用することにより耐熱性を向上させる発明がなされた（例えば、特許文献３参照）。この方法を用いると、確かにポリマーの耐熱性に一定の向上は見られるものの、チタン化合物の重合活性の高さに起因して分解反応も促進されるため、そのレベルは必ずしも十分とはいえない。さらにリン化合物をある添加量以上加えるとチタン化合物の重合活性が低下し、目標の重合度まで到達しなかったり、重合時間が著しく伸びてしまい、生産性が悪化してしまう問題があり、優れた重合活性と十分な耐熱性を両立するまでには至っていない。 On the other hand, in order to solve the problem of degradation and degradation, an invention was made to improve heat resistance by using a titanium compound and a phosphorus compound in combination (for example, see Patent Document 3). If this method is used, a certain improvement in the heat resistance of the polymer is certainly observed, but the decomposition reaction is also promoted due to the high polymerization activity of the titanium compound, so the level is not necessarily sufficient. . Furthermore, when a phosphorus compound is added in a certain amount or more, the polymerization activity of the titanium compound is lowered, and the target polymerization degree is not reached, the polymerization time is remarkably increased, and there is a problem that productivity is deteriorated. It has not yet achieved both polymerization activity and sufficient heat resistance.
特開平９－２２７７６７号公報JP-A-9-227767 特開平８－７３７１９号公報JP-A-8-73719 特開平６－１００６８０号公報JP-A-6-1000068
　本発明は、かかる従来技術の課題を背景になされたものである。すなわち、本発明の目的は低温での成形を可能にし、熱分解によるカルボキシル基の生成を抑制すること、さらには触媒となる金属化合物の添加量を、高い重合活性を保持しながら可能な限り少なくすることにより、優れた長期耐熱性を得ることである。 The present invention has been made against the background of the problems of the prior art. That is, the object of the present invention is to enable molding at a low temperature, suppress the formation of carboxyl groups by thermal decomposition, and further reduce the addition amount of a metal compound as a catalyst as much as possible while maintaining high polymerization activity. It is to obtain excellent long-term heat resistance.
　本願発明者は、上記課題を解決するため、鋭意検討を行なった結果、ポリエステルの残存金属元素が熱劣化、加水分解に影響を及ぼすことを感知し、残存金属元素量を極めて低濃度とすることで、太陽電池裏面封止用等の屋外用途として、優れた長期耐熱性を奏するという効果を見出し、本願発明に至ったものである。すなわち、本発明の構成は下記のとおりである。 As a result of intensive studies to solve the above problems, the present inventor senses that the residual metal element of the polyester affects thermal degradation and hydrolysis, and makes the amount of the residual metal element extremely low. Thus, the present invention has found the effect of exhibiting excellent long-term heat resistance for outdoor use such as solar cell back surface sealing, and has led to the present invention. That is, the configuration of the present invention is as follows.
［１］ジカルボン酸成分とグリコール成分からなるポリエステル樹脂であって、ジカルボン酸成分としてフランジカルボン酸を１０モル％以上含み、下記要件（１）～（３）を満たすポリエステル樹脂。
（１）全金属元素含有量がポリエステル樹脂の質量に対して１５０ｐｐｍ以下であること
（２）リン元素含有量がポリエステル樹脂の質量に対して１００ｐｐｍ以下であること
（３）下記式で表されるＴＯＤΔ還元粘度が０．０３０ｄｌ／ｇ以下であること
（ＴＯＤΔ還元粘度）＝（熱酸化試験前の還元粘度）－（熱酸化試験後の還元粘度）
（ここで、熱酸化試験とは、空気下、ポリエステル樹脂の融点＋３０℃の温度で２分間溶融後、同温度で１分間、荷重（１００ｋｇｆ／ｃｍ２）下に置く熱履歴を与えたポリエステル樹脂試料を、空気下、１８０℃の温度で６０分間加熱処理する試験である。）
［２］ポリエステル重合時の触媒が、アルミニウム化合物及びリン化合物である［１］に記載のポリエステル樹脂。
［３］融点が２２０℃以下である［１］～［２］のいずれかに記載のポリエステル樹脂。
［４］［１］～［３］のいずれかに記載のポリエステル樹脂を用いたフィルム。
［５］［１］～［３］のいずれかに記載のポリエステル樹脂を用いたシート。
［６］［１］～［３］のいずれかに記載のポリエステル樹脂を用いた射出成形体。 [1] A polyester resin comprising a dicarboxylic acid component and a glycol component, comprising 10 mol% or more of furandicarboxylic acid as a dicarboxylic acid component and satisfying the following requirements (1) to (3):
(1) The total metal element content is 150 ppm or less with respect to the mass of the polyester resin. (2) The phosphorus element content is 100 ppm or less with respect to the mass of the polyester resin. (3) TODΔreduced viscosity is 0.030 dl / g or less (TODΔreduced viscosity) = (reduced viscosity before thermal oxidation test) − (reduced viscosity after thermal oxidation test)
(Here, the thermal oxidation test is a polyester resin that has been melted for 2 minutes at a temperature of the melting point of the polyester resin + 30 ° C. in air and then given a thermal history under the load (100 kgf / cm 2 ) for 1 minute at the same temperature) This is a test in which a sample is heat-treated at 180 ° C. for 60 minutes in air.)
[2] The polyester resin according to [1], wherein the catalyst at the time of polyester polymerization is an aluminum compound and a phosphorus compound.
[3] The polyester resin according to any one of [1] to [2], which has a melting point of 220 ° C. or lower.
[4] A film using the polyester resin according to any one of [1] to [3].
[5] A sheet using the polyester resin according to any one of [1] to [3].
[6] An injection molded article using the polyester resin according to any one of [1] to [3].
　本発明のポリエステル樹脂は、長期熱安定性に優れる。よって、屋外で使用される太陽電池用途等の構成部材として有用である。 The polyester resin of the present invention is excellent in long-term thermal stability. Therefore, it is useful as a constituent member for solar cell applications used outdoors.
　本発明のポリエステル樹脂は、ポリエステルに触媒（金属元素）を含むものであり、一種の組成物であるが、触媒は微量であることから「樹脂」として表す。本発明のポリエステル樹脂は、全金属元素含有量がポリエステル樹脂の質量に対して１５０ｐｐｍ以下であること特徴とする。ポリエステル中に多くの金属が含有すると、高温下でポリエステルの熱分解反応を促進し、ポリエステルの熱劣化を引き起こす要因となりうる。そこで、本発明では、ポリエステル樹脂の長期熱安定性を保持する点から、金属元素の含有量を１５０ｐｐｍ以下にする。さらに、前記金属元素の含有量は、１００ｐｐｍ以下が好ましく、８０ｐｐｍ以下がより好ましく、５０ｐｐｍ以下がさらに好ましい。ポリエステル樹脂の熱劣化を低減する点からは前記金属元素の含有量は少ない方が良いが、ポリエステル製造時において重合反応を促進するために、触媒として前記濃度範囲内で遷移金属もしく典型金属元素を添加することが望ましい。そのため、前記金属元素の含有量の下限は、１ｐｐｍ以上が好ましく、５ｐｐｍ以上がより好ましく、１０ｐｐｍ以上がさらに好ましい。ポリエステルの生産性の点から、上記含有量の範囲内でありながら、十分な触媒活性を奏するためには、後述するように適切な触媒種を選定することが望ましい。 The polyester resin of the present invention contains a catalyst (metal element) in polyester and is a kind of composition, but the catalyst is expressed as “resin” because the amount of the catalyst is small. The polyester resin of the present invention is characterized in that the total metal element content is 150 ppm or less with respect to the mass of the polyester resin. When a lot of metals are contained in the polyester, the thermal decomposition reaction of the polyester is accelerated at a high temperature, which may cause thermal degradation of the polyester. Therefore, in the present invention, the content of the metal element is set to 150 ppm or less from the viewpoint of maintaining the long-term thermal stability of the polyester resin. Furthermore, the content of the metal element is preferably 100 ppm or less, more preferably 80 ppm or less, and further preferably 50 ppm or less. From the viewpoint of reducing the thermal deterioration of the polyester resin, the content of the metal element is preferably small. However, in order to promote the polymerization reaction during the production of the polyester, a transition metal or typical metal element is used as a catalyst within the concentration range. It is desirable to add. Therefore, the lower limit of the content of the metal element is preferably 1 ppm or more, more preferably 5 ppm or more, and further preferably 10 ppm or more. From the viewpoint of polyester productivity, it is desirable to select an appropriate catalyst type as described later in order to achieve sufficient catalytic activity while being within the above-mentioned content range.
　本発明のポリエステル樹脂とは、ジカルボン酸成分とグリコール成分から主として構成され、必要に応じて３官能以上の成分が共重合されたものである。 The polyester resin of the present invention is mainly composed of a dicarboxylic acid component and a glycol component, and is obtained by copolymerizing three or more functional components as necessary.
　本発明のポリエステル樹脂には、フランジカルボン酸成分が共重合されている。フランジカルボン酸成分は芳香環構造を有しながら、ポリエステル樹脂の原料としてよく用いられるテレフタル酸と比較して、共重合することにより樹脂の融点を下げる効果がある。樹脂を成形する際には成形温度を樹脂の融点以上に設定する必要があるが、フランジカルボン酸の共重合により成形温度を低く設定できるため、熱分解によるカルボキシル基の生成が抑制され、良好な長期熱安定性を得ることができる。フランジカルボン酸は、反応性、ポリマー鎖の立体構造等を考慮すると、その異性体の中でも、特に２，５－フランジカルボン酸が好ましい。 In the polyester resin of the present invention, a furan carboxylic acid component is copolymerized. While the furancarboxylic acid component has an aromatic ring structure, it has the effect of lowering the melting point of the resin by copolymerization, compared with terephthalic acid, which is often used as a raw material for polyester resins. When molding the resin, it is necessary to set the molding temperature to be equal to or higher than the melting point of the resin, but since the molding temperature can be set low by copolymerization of flange carboxylic acid, the formation of carboxyl groups due to thermal decomposition is suppressed, which is good. Long-term thermal stability can be obtained. In view of reactivity, the three-dimensional structure of the polymer chain, etc., 2,5-furandicarboxylic acid is particularly preferable among the isomers.
　本発明のポリエステル樹脂に用いられるフランジカルボン酸の共重合比率は、全ジカルボン酸成分に対して、１０モル％以上共重合することが必要であり、１５モル％以上が好ましく、２０モル％以上がさらに好ましく、５０モル％以上が特に好ましく、１００モル％としても差し支えない。１０モル％未満であると、融点を下げる効果がほとんどないので好ましくない。 The copolymerization ratio of furandicarboxylic acid used in the polyester resin of the present invention is required to be 10 mol% or more, preferably 15 mol% or more, more preferably 20 mol% or more with respect to the total dicarboxylic acid component. More preferably, it is particularly preferably 50 mol% or more, and may be 100 mol%. If it is less than 10 mol%, there is almost no effect of lowering the melting point, which is not preferable.
　本発明のポリエステル樹脂に用いられるフランジカルボン酸以外のジカルボン酸成分としては特に制限されず、テレフタル酸やイソフタル酸、フタル酸、ナフタレンジカルボン酸、４、４’－ジカルボキシビフェニル、５－ナトリウムスルホイソフタル酸等の芳香族ジカルボン酸、１，４－シクロヘキサンジカルボン酸、１，３－シクロヘキサンジカルボン酸、１，２－シクロヘキサンジカルボン酸、２，５－ノルボルネンジカルボン酸、テトラヒドロフタル酸等の脂環族ジカルボン酸や、シュウ酸、マロン酸、コハク酸、アジピン酸、アゼライン酸、セバシン酸、ウンデカン二酸、ドデカン二酸、オクタデカン二酸、フマル酸、マレイン酸、イタコン酸、メサコン酸、シトラコン酸、ダイマー酸等の脂肪族ジカルボン酸等が挙げられる。このうち、脂肪族ジカルボン酸成分を用いると、さらに融点が低下し、耐熱性が著しく低下する場合があるため、芳香族ジカルボン酸を使用することが好ましい。中でも、汎用性、耐熱性の観点からテレフタル酸、２，６－ナフタレンジカルボン酸がより好ましい。これらのうち、一種類、もしくは二種類以上を共重合することができる。 The dicarboxylic acid component other than furandicarboxylic acid used in the polyester resin of the present invention is not particularly limited, and is terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, 4,4′-dicarboxybiphenyl, 5-sodium sulfoisophthalate. Aromatic dicarboxylic acids such as acids, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 2,5-norbornenedicarboxylic acid, tetrahydrophthalic acid, etc. Oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, octadecanedioic acid, fumaric acid, maleic acid, itaconic acid, mesaconic acid, citraconic acid, dimer acid, etc. And aliphatic dicarboxylic acids. Among these, when an aliphatic dicarboxylic acid component is used, it is preferable to use an aromatic dicarboxylic acid because the melting point is further lowered and the heat resistance may be significantly lowered. Among these, terephthalic acid and 2,6-naphthalenedicarboxylic acid are more preferable from the viewpoint of versatility and heat resistance. Among these, one type or two or more types can be copolymerized.
　本発明のポリエステル樹脂に用いられるグリコール成分としては特に制限はないが、エチレングリコール、１，２－プロパンジオール、１，３－プロパンジオール、１，２－ブタンジオール、１，３－ブタンジオール、１，４－ブタンジオール、２－メチル－１，３－プロパンジオール、２－アミノ－２－エチル－１，３－プロパンジオール、２－アミノ－２－メチル－１，３－プロパンジオール、１，１０－デカンジオール、ジメチロールトリシクロデカン、ジエチレングリコール、トリエチレングリコール等の脂肪族グリコール、ビスフェノールＡ、ビスフェノールＳ、ビスフェノールＣ、ビスフェノールＺ、ビスフェノールＡＰ、４，４′－ビフェノールのエチレンオキサイド付加体またはプロピレンオキサイド付加体、１，２－シクロヘキサンジメタノール、１，３－シクロヘキサンジメタノール、１，４－シクロヘキサンジメタノール等の脂環族グリコール、ポリエチレングリコール、ポリプロピレングリコール等が挙げられる。中でも、汎用性、耐熱性の観点からエチレングリコールが好ましい。 The glycol component used in the polyester resin of the present invention is not particularly limited, but ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, , 4-butanediol, 2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, 1,10 -Aliphatic glycols such as decanediol, dimethylol tricyclodecane, diethylene glycol, triethylene glycol, bisphenol A, bisphenol S, bisphenol C, bisphenol Z, bisphenol AP, ethylene oxide adducts or propylene oxide of 4,4'-biphenol Adduct, 1,2-si B hexane dimethanol, 1,3-cyclohexane dimethanol, an alicyclic glycol such as 1,4-cyclohexane dimethanol, polyethylene glycol, polypropylene glycol, and the like. Among these, ethylene glycol is preferable from the viewpoint of versatility and heat resistance.
　本発明のポリエステル樹脂には、機械的強度等の機能性を高めるため、必要に応じて３官能以上のカルボン酸や３官能以上のアルコール成分を共重合することができる。３官能以上のモノマーの共重合比率としては、全ジカルボン酸成分１００モル％または全グリコール成分１００モル％に対して０．２～５モル％程度が適当である。３官能以上のモノマーの共重合比率が低すぎると共重合した効果が発現せず、共重合比率が高すぎる場合には、ゲル化が問題になる場合がある。３官能以上のカルボン酸にはトリメリット酸、ピロメリット酸、ベンゾフェノンテトラカルボン酸、無水トリメリット酸、無水ピロメリット酸、無水ベンゾフェノンテトラカルボン酸、トリメシン酸等の芳香族カルボン酸、１，２，３，４－ブタンテトラカルボン酸等の脂肪族カルボン酸が挙げられる。３官能以上のアルコール成分にはグリセロール、トリメチロールプロパン、トリメチロールエタン、ペンタエリスリトール、α－メチルグルコース、マニトール、ソルビトールが挙げられる。 The polyester resin of the present invention can be copolymerized with a trifunctional or higher functional carboxylic acid or a trifunctional or higher functional alcohol component as necessary in order to enhance the functionality such as mechanical strength. The copolymerization ratio of the tri- or higher functional monomer is suitably about 0.2 to 5 mol% with respect to 100 mol% of all dicarboxylic acid components or 100 mol% of all glycol components. If the copolymerization ratio of the trifunctional or higher monomer is too low, the effect of copolymerization is not exhibited, and if the copolymerization ratio is too high, gelation may be a problem. Tri- or higher functional carboxylic acids include trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid, trimesic acid and other aromatic carboxylic acids, 1, 2, Examples include aliphatic carboxylic acids such as 3,4-butanetetracarboxylic acid. Examples of the tri- or higher functional alcohol component include glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, α-methylglucose, mannitol, and sorbitol.
　さらに、本発明のポリエステル樹脂には、ヒドロキシカルボン酸、ラクトン類、モノカルボン酸及びモノアルコールを共重合成分として用いてもよい。これら共重合成分の共重合比率としては、全ジカルボン酸成分１００モル％または全グリコール成分１００モル％に対して５モル％以下程度が適当である。ヒドロキシカルボン酸の例としては、ｐ－ヒドロキシ安息香酸、ｍ－ヒドロキシ安息香酸、ｏ－ヒドロキシ安息香酸、乳酸、グリコール酸、２－ヒドロキシ酪酸、３－ヒドロキシ酪酸、４－ヒドロキシ酪酸、２－ヒドロキシイソ酪酸、２－ヒドロキシ－２－メチル酪酸、２－ヒドロキシ吉草酸、３－ヒドロキシ吉草酸、４－ヒドロキシ吉草酸、５－ヒドロキシ吉草酸、６－ヒドロキシカプロン酸、１０－ヒドロキシステアリン酸等が挙げられる。ラクトン類の例としては、β－プロピオラクトン、β－ブチロラクトン、γ－ブチロラクトン、δ－バレロラクトン、ε－カプロラクトン等があげられる。また、モノカルボン酸の例としては、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、リノール酸、リノレン酸、安息香酸、ｐ－ｔｅｒｔ－ブチル安息香酸、シクロヘキサン酸、４－ヒドロキシフェニルステアリン酸等、モノアルコールとしては、オクチルアルコール、デシルアルコール、ラウリルアルコール、ミリスチルアルコール、セチルアルコール、ステアリルアルコール、２－フェノキシエタノール等が挙げられる。 Furthermore, hydroxycarboxylic acids, lactones, monocarboxylic acids and monoalcohols may be used as copolymerization components in the polyester resin of the present invention. The copolymerization ratio of these copolymerization components is suitably about 5 mol% or less with respect to 100 mol% of all dicarboxylic acid components or 100 mol% of all glycol components. Examples of hydroxycarboxylic acids include p-hydroxybenzoic acid, m-hydroxybenzoic acid, o-hydroxybenzoic acid, lactic acid, glycolic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxyiso Examples include butyric acid, 2-hydroxy-2-methylbutyric acid, 2-hydroxyvaleric acid, 3-hydroxyvaleric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, 6-hydroxycaproic acid, and 10-hydroxystearic acid. . Examples of lactones include β-propiolactone, β-butyrolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, and the like. Examples of monocarboxylic acids include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, p-tert-butylbenzoic acid, cyclohexane acid, 4-hydroxyphenyl stearic acid. Examples of the monoalcohol such as acid include octyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, 2-phenoxyethanol and the like.
　ポリエステル樹脂の重合方法は、ジエステルカルボン酸成分とグリコール成分を出発物質とするエステル交換法、ジカルボン酸成分とグリコール成分を出発物質とする直接エステル化法がある。エステル交換法では、生産性を確保するためエステル交換時にＺｎ、Ｃａ、Ｍｇ等の触媒を添加するため、前記濃度範囲を満たさないことがある。よって本発明におけるポリエステルの重合方法は直接エステル化法が好ましい。 Polyester resin polymerization methods include a transesterification method using a diester carboxylic acid component and a glycol component as starting materials, and a direct esterification method using a dicarboxylic acid component and a glycol component as starting materials. In the transesterification method, a catalyst such as Zn, Ca, Mg, etc. is added at the time of transesterification in order to ensure productivity, so the concentration range may not be satisfied. Therefore, the direct esterification method is preferred as the polyester polymerization method in the present invention.
　フランジカルボン酸を用いて、少量の金属量で反応性を確保するには、重縮合前のオリゴマー物性が重要である。具体的には、エステル化を無触媒で実施し、エステル化後に触媒を添加し攪拌により均一化後、オリゴマー酸価が１００ｅｑ／ｔｏｎ以上の段階で重縮合工程に入ることが好ましい。オリゴマー酸価が１００ｅｑ／ｔｏｎ以上であれば、金属の触媒活性に加え、オリゴマーのプロトンが重縮合触媒として働き生産性を確保できる。オリゴマー酸価は、２００ｅｑ／ｔｏｎ以上が好ましく、３００ｅｑ／ｔｏｎ以上がさらに好ましい。プロトンの触媒能という点では、オリゴマー酸価が高ければ高いほど好ましいが、オリゴマー酸価が６００ｅｑ／ｔｏｎを超えるとエステル化不良により重合が進行せず、分子量が上がらないことがある。 In order to ensure reactivity with a small amount of metal using furandicarboxylic acid, oligomer physical properties before polycondensation are important. Specifically, it is preferable to carry out esterification without a catalyst, add a catalyst after esterification, homogenize by stirring, and then enter the polycondensation step at a stage where the oligomer acid value is 100 eq / ton or more. When the oligomer acid value is 100 eq / ton or more, in addition to the catalytic activity of the metal, the proton of the oligomer acts as a polycondensation catalyst to ensure productivity. The oligomer acid value is preferably 200 eq / ton or more, and more preferably 300 eq / ton or more. In terms of proton catalytic ability, the higher the oligomer acid value, the better. However, when the oligomer acid value exceeds 600 eq / ton, polymerization may not proceed due to poor esterification, and the molecular weight may not increase.
　本発明のポリエステル樹脂を重合する際の、重合触媒としては、環境負荷の点から重金属でないことが好ましく、重合活性、ポリエステルの物性の面からアルミニウム化合物であることがさらに好ましい。 In the polymerization of the polyester resin of the present invention, the polymerization catalyst is preferably not a heavy metal from the viewpoint of environmental burden, and more preferably an aluminum compound from the viewpoint of polymerization activity and polyester physical properties.
　前記アルミニウム化合物として、公知のアルミニウム化合物を使用することができる。 As the aluminum compound, a known aluminum compound can be used.
　アルミニウム化合物としては、具体的には、ギ酸アルミニウム、酢酸アルミニウム、塩基性酢酸アルミニウム、プロピオン酸アルミニウム、蓚酸アルミニウム等のカルボン酸塩、塩化アルミニウム、水酸化アルミニウム、水酸化塩化アルミニウム等の無機酸塩、アルミニウムメトキサイド、アルミニウムエトキサイド、アルミニウムｉｓｏ‐プロポキサイド、アルミニウムｎ‐ブトキサイド、アルミニウムｔ－ブトキサイド等アルミニウムアルコキサイド、アルミニウムアセチルアセトネート、アルミニウムアセチルアセテート、等のアルミニウムキレート化合物、トリメチルアルミニウム、トリエチルアルミニウム等の有機アルミニウム化合物及びこれらの部分加水分解物、酸化アルミニウム等が挙げられる。これらのうちカルボン酸塩、無機酸塩及びキレート化合物が好ましく、これらの中でもさらに酢酸アルミニウム、塩基性酢酸アルミニウム、塩化アルミニウム、水酸化アルミニウム、水酸化塩化アルミニウム及びアルミニウムアセチルアセトネートが特に好ましい。 Specific examples of aluminum compounds include carboxylates such as aluminum formate, aluminum acetate, basic aluminum acetate, aluminum propionate, and aluminum oxalate; inorganic acid salts such as aluminum chloride, aluminum hydroxide, and aluminum hydroxide chloride; Aluminum methoxide, aluminum ethoxide, aluminum iso-propoxide, aluminum n-butoxide, aluminum t-butoxide and other aluminum alkoxides, aluminum acetylacetonate, aluminum acetylacetate, etc. Examples include organoaluminum compounds, partial hydrolysates thereof, and aluminum oxide. Of these, carboxylates, inorganic acid salts and chelate compounds are preferred, and among these, aluminum acetate, basic aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetylacetonate are particularly preferred.
　ただし、アルミニウム化合物単独では重合活性が低く、生産性を確保するためにはポリエステルのジカルボン酸や多価カルボン酸等のカルボン酸成分の全構成ユニットに対して１５０ｐｐｍ以上添加する必要がある。そこで、全金属元素含有量がポリエステルに対して１５０ｐｐｍ以下とするためには、重合活性を上昇させる目的で助触媒としてリン化合物を添加することが好ましい。 However, the polymerization activity of the aluminum compound alone is low, and in order to ensure productivity, it is necessary to add 150 ppm or more with respect to all constituent units of the carboxylic acid component such as polyester dicarboxylic acid or polyvalent carboxylic acid. Therefore, in order to control the total metal element content to 150 ppm or less with respect to the polyester, it is preferable to add a phosphorus compound as a promoter for the purpose of increasing the polymerization activity.
　本発明において、上記助触媒として用いるべきリン化合物の濃度は、リン元素含有量としてポリエステル樹脂の質量に対して１００ｐｐｍ以下であることが好ましい。ポリエステルに対するリン元素含有量が上記範囲を超えると、ポリエステルの重合反応においてリン化合物がポリエステルの主鎖に組み込まれ、ポリエステルの耐久性が低下する場合がある。上記ポリエステルに対するリン元素含有量は、９５ｐｐｍ以下であることがより好ましく、９０ｐｐｍ以下であることがさらに好ましい。また、上記助触媒として用いる場合、重合活性を上昇させる目的から、リン元素含有量は１ｐｐｍ以上であることが好ましく、３ｐｐｍ以上であることがさらに好ましい。なお、本発明において用いられるべき好ましいリン化合物の種類及びその添加量は後述するが、その際、リン化合物の添加量としては、カルボン酸成分の全構成ユニットに対する添加量として表示する。 In the present invention, the concentration of the phosphorus compound to be used as the cocatalyst is preferably 100 ppm or less as the phosphorus element content with respect to the mass of the polyester resin. When the phosphorus element content with respect to the polyester exceeds the above range, the phosphorus compound may be incorporated into the main chain of the polyester in the polyester polymerization reaction, and the durability of the polyester may be reduced. The phosphorus element content relative to the polyester is more preferably 95 ppm or less, and even more preferably 90 ppm or less. When used as the cocatalyst, the phosphorus element content is preferably 1 ppm or more and more preferably 3 ppm or more for the purpose of increasing the polymerization activity. In addition, although the kind and the addition amount of the preferable phosphorus compound which should be used in this invention are mentioned later, it displays as an addition amount with respect to all the structural units of a carboxylic acid component as the addition amount of a phosphorus compound in that case.
　上記助触媒として用いるリン化合物は特に限定はされないが、ホスホン酸系化合物、ホスフィン酸系化合物からなる群より選ばれる一種または二種以上の化合物を用いると触媒活性の向上効果が大きく好ましい。これらの中でも、一種または二種以上のホスホン酸系化合物を用いると触媒活性の向上効果が特に大きく好ましい。なかでも、ポリエステルの熱酸化安定性を向上の点から、フェノール部を同一分子内に有するリン化合物が特に好ましい。 The phosphorus compound used as the co-catalyst is not particularly limited, but it is preferable to use one or more compounds selected from the group consisting of phosphonic acid compounds and phosphinic acid compounds because the effect of improving the catalytic activity is great. Among these, when one or two or more phosphonic acid compounds are used, the effect of improving the catalytic activity is particularly large and preferable. Especially, the phosphorus compound which has a phenol part in the same molecule from the point of improving the thermal oxidation stability of polyester is especially preferable.
　本発明のポリエステル樹脂は、助触媒として使用するフェノール部位含有のリン化合物としては、具体的には、３、５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジルホスホン酸エチル、３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジルホスホン酸メチル、３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジルホスホン酸イソプロピル、３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジルホスホン酸フェニル、３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジルホスホン酸オクタデシル、３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジルホスホン酸、リチウム［３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジルホスホン酸エチル］、ナトリウム［３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジルホスホン酸エチル］、ナトリウム［３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジルホスホン酸］、カルシウムビス［３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジルホスホン酸エチル］、カルシウムビス［３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジルホスホン酸］、３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジルホスホン酸ジエチル、３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジルホスホン酸ジフェニルが挙げられる。これらのうちＩｒｇａｎｏｘ１２２２（ＢＡＳＦ社製）として市販されている３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジルホスホン酸ジエチル、また、Ｉｒｇａｎｏｘ１４２５（ＢＡＳＦ社製）として市販されているカルシウムビス［３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジルホスホン酸エチル］が特に好ましい。 The polyester resin of the present invention is, as a phosphorus compound containing a phenol moiety used as a co-catalyst, specifically 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid ethyl, 3,5-di- methyl tert-butyl-4-hydroxybenzylphosphonate, isopropyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, phenyl 3,5-di-tert-4-butyl-4-hydroxybenzylphosphonate, 3, Octadecyl 5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, lithium [3,5-di-tert-butyl-4-hydroxybenzylphosphone Acid ethyl], sodium [3,5-di-tert-butyl-4-hydroxy Ethyl benzylphosphonate], sodium [3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid], calcium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid ethyl], calcium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid], diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-hydroxy And diphenyl benzylphosphonate. Of these, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate commercially available as Irganox 1222 (manufactured by BASF), and calcium bis [3, commercially available as Irganox 1425 (manufactured by BASF) Particularly preferred is ethyl 5-di-tert-butyl-4-hydroxybenzylphosphonate.
　本発明のポリエステルはチタンを触媒とすることもできる。チタンを触媒として用いる場合も少量の添加量で生産性を確保できるが、チタンは触媒活性が高いため、加熱下でポリエステルの熱酸化劣化が生じやすくなり、長期の熱安定性を得られない場合がある。そのため、本発明においてはポリエステルの触媒種としてチタン以外の触媒種を用いることが好ましい。 The polyester of the present invention can also use titanium as a catalyst. Even when titanium is used as a catalyst, productivity can be secured with a small amount of addition, but titanium has high catalytic activity, so thermal oxidation degradation of polyester tends to occur under heating, and long-term thermal stability cannot be obtained. There is. Therefore, in the present invention, it is preferable to use a catalyst species other than titanium as the polyester catalyst species.
　本発明のポリエステル樹脂は、前述の触媒種を用いて好適に得ることができるため、ポリエステル樹脂に対する全金属元素量を１５０ｐｐｍ以下にすることができる。そのため、本発明のポリエステル樹脂は熱酸化安定性に優れ、長期にわたる熱安定性を奏することが可能となる。本発明のポリエステル樹脂は、熱酸化安定性の指標である、下記式で表されるＴＯＤΔ還元粘度が０．０３０ｄｌ／ｇ以下を満たす。
（ＴＯＤΔ還元粘度）＝（熱酸化試験前の還元粘度）－（熱酸化試験後の還元粘度）
（ここで、熱酸化試験とは、空気下、ポリエステル樹脂の融点＋３０℃の温度で２分間溶融後、同温度で１分間、荷重（１００ｋｇｆ／ｃｍ２）下に置く熱履歴を与えたポリエステル樹脂試料を、空気下、１８０℃の温度で６０分間加熱処理する試験である。） Since the polyester resin of the present invention can be suitably obtained by using the above-mentioned catalyst species, the total metal element amount relative to the polyester resin can be made 150 ppm or less. Therefore, the polyester resin of the present invention is excellent in thermal oxidation stability and can exhibit long-term thermal stability. The polyester resin of the present invention satisfies a TODΔ reduced viscosity represented by the following formula, which is an index of thermal oxidation stability, of 0.030 dl / g or less.
(TODΔ reduced viscosity) = (reduced viscosity before thermal oxidation test) − (reduced viscosity after thermal oxidation test)
(Here, the thermal oxidation test is a polyester resin that has been melted for 2 minutes at a temperature of the melting point of the polyester resin + 30 ° C. in air and then given a thermal history under the load (100 kgf / cm 2 ) for 1 minute at the same temperature) This is a test in which a sample is heat-treated at 180 ° C. for 60 minutes in air.)
　熱酸化試験について、詳細に説明する。熱酸化試験とは、空気下、ポリエステル樹脂の融点＋３０℃の温度で２分間溶融後、同温度で１分間、荷重（１００ｋｇｆ／ｃｍ２）下に置く熱履歴を与えたポリエステル樹脂試料を凍結粉砕して、１００メッシュ以下の粉末とし、７０℃で１２時間、１Ｔｏｒｒ以下で真空乾燥した後、これを０．３ｇ秤量し、ガラス試験管に入れ、空気下、１８０℃の温度で６０分間加熱処理する試験である。
　熱酸化試験において、ポリエステル樹脂試料を凍結粉砕する前に、熱履歴を与える目的でポリエステル樹脂の融点＋３０℃の温度でヒートプレスシートを作製する必要がある。具体的には、１．０ｇのポリエステル樹脂を２枚のテフロン（登録商標）シートの間に挟み、さらにそれを２枚のステンレス板に挟んでヒートプレス機に設置し、ポリエステル樹脂の融点＋３０℃の温度で２分間溶融後、１００ｋｇｆ／ｃｍ２の荷重をかけ、１分後に水につけて急冷してサンプルを作製する。この熱履歴を与えたシートサンプルを凍結粉砕に用いる必要がある。
　これは成形時の熱分解によるカルボキシル基の生成をモデル的に再現したものであり、フランジカルボン酸成分を含み、全金属元素含有量が少ない本発明のポリエステル樹脂は、このカルボキシル基の生成が効果的に抑制されるため、熱酸化試験における粘度低下を抑制することができる。 The thermal oxidation test will be described in detail. The thermal oxidation test is a method of freeze-pulverizing a polyester resin sample that has been melted for 2 minutes at a temperature of the melting point of the polyester resin + 30 ° C. in air and then given a thermal history for 1 minute under the load (100 kgf / cm 2 ). Then, after making powder of 100 mesh or less and vacuum-drying at 70 ° C. for 12 hours and 1 Torr or less, 0.3 g of this was weighed, put into a glass test tube, and heated in air at a temperature of 180 ° C. for 60 minutes. It is a test to do.
In the thermal oxidation test, before freeze-pulverizing a polyester resin sample, it is necessary to produce a heat press sheet at a temperature of the melting point of the polyester resin + 30 ° C. for the purpose of giving a thermal history. Specifically, 1.0 g of polyester resin is sandwiched between two Teflon (registered trademark) sheets, and is further sandwiched between two stainless steel plates and installed in a heat press machine. The melting point of the polyester resin + 30 ° C. After melting at a temperature of 2 minutes, a load of 100 kgf / cm 2 is applied, and after 1 minute, it is immersed in water and rapidly cooled to prepare a sample. It is necessary to use the sheet sample provided with this thermal history for freeze pulverization.
This is a model reproduction of the formation of carboxyl groups by thermal decomposition during molding, and the polyester resin of the present invention containing a furandicarboxylic acid component and a low content of all metal elements is effective for the generation of carboxyl groups. Therefore, the viscosity reduction in the thermal oxidation test can be suppressed.
　熱酸化分解にはカルボキシル基の生成を伴うため、分解速度は一定でなく、ＴＯＤΔ還元粘度が大きくなるほど、分解は加速的に進行する。前記ＴＯＤΔ還元粘度が０．０３０ｄｌ／ｇ以下であれば、屋外で使用することは可能であるが、好ましくは０．０２５ｄｌ／ｇ以下、より好ましくは０．０２０ｄｌ／ｇ以下、下限は０である。ＴＯＤΔ還元粘度が０．０２０ｄｌ／ｇ以下であると、分解速度の進行が抑制されるため、望ましい。 Since the thermal oxidative decomposition involves the formation of carboxyl groups, the decomposition rate is not constant, and the decomposition proceeds at an accelerated rate as the TODΔ reduced viscosity increases. If the TODΔ reduced viscosity is 0.030 dl / g or less, it can be used outdoors, but preferably 0.025 dl / g or less, more preferably 0.020 dl / g or less, and the lower limit is 0. . A TODΔreduced viscosity of 0.020 dl / g or less is desirable because the progress of the decomposition rate is suppressed.
　全金属含有量は少なければ少ないほど、熱酸化安定性に有利である。しかし、金属含有量が少ない即ち触媒量が少ない場合は、生産性の面では不利となる。そこで少量のアルミニウム化合物と助触媒であるリン化合物を併用し、重合活性を確保することが好ましい。さらにリン化合物はフェノール部位を持つことが好ましい。フェノール部位含有のリン化合物は、酸素下でラジカル機構により分解するポリエステル劣化を抑制する効果を有するためである。この機能を高めるためには、フェノール部位が立体的、電子的に安定化され、よりラジカルトラップ能を発現するヒンダートフェノール骨格を有することがより好ましい。 The smaller the total metal content, the more advantageous the thermal oxidation stability. However, when the metal content is small, that is, the catalyst amount is small, it is disadvantageous in terms of productivity. Therefore, it is preferable to use a small amount of an aluminum compound and a phosphorus compound as a cocatalyst together to ensure polymerization activity. Further, the phosphorus compound preferably has a phenol moiety. This is because the phosphorus compound containing a phenol moiety has an effect of suppressing polyester degradation that is decomposed by a radical mechanism under oxygen. In order to enhance this function, it is more preferable that the phenol moiety has a hindered phenol skeleton that is sterically and electronically stabilized and expresses more radical trapping ability.
　本発明のポリエステル樹脂の還元粘度は特に制限はないが、０．１～２．０ｄｌ／ｇであることが望ましい。０．１ｄｌ／ｇ未満であると、機械的強度が著しく低下し、実用的に使用困難となる。２．０ｄｌ／ｇ超であると、溶融粘度が高くなるためにハンドリング性が悪くなるほか、重合時間が長くなるため生産性に悪影響を及ぼす可能性がある。好ましくは０．２～１．８ｄｌ／ｇ、より好ましくは０．３～１．５ｄｌ／ｇである。 The reduced viscosity of the polyester resin of the present invention is not particularly limited, but is preferably 0.1 to 2.0 dl / g. If it is less than 0.1 dl / g, the mechanical strength is remarkably lowered and it becomes practically difficult to use. If it exceeds 2.0 dl / g, the melt viscosity becomes high and the handling property becomes poor, and the polymerization time becomes long, which may adversely affect productivity. It is preferably 0.2 to 1.8 dl / g, more preferably 0.3 to 1.5 dl / g.
　本発明のポリエステル樹脂には、高温高湿下で分解劣化が起きた際に生成するカルボキシル基を封鎖するために、カルボジイミド化合物やオキサゾリン化合物、エポキシ化合物等の末端封鎖剤を任意の割合で配合してもよい。 In the polyester resin of the present invention, a terminal blocking agent such as a carbodiimide compound, an oxazoline compound, or an epoxy compound is blended at an arbitrary ratio in order to block a carboxyl group that is generated when decomposition degradation occurs at high temperature and high humidity. May be.
　本発明のポリエステル樹脂をより高性能なものにするため、一般に良く知られている、安定剤、滑剤、離型剤、可塑剤、難燃剤、難燃助剤、紫外線吸収剤、光安定剤、顔料、染料、帯電防止剤、導電性付与剤、分散剤、相溶化剤、抗菌剤、各種フィラー等を、単独又は二種類以上を組み合わせて添加することができる。 In order to make the polyester resin of the present invention higher performance, generally well known stabilizers, lubricants, mold release agents, plasticizers, flame retardants, flame retardant aids, ultraviolet absorbers, light stabilizers, Pigments, dyes, antistatic agents, conductivity-imparting agents, dispersants, compatibilizing agents, antibacterial agents, various fillers, and the like can be added alone or in combination of two or more.
　本発明のポリエステル樹脂は、公知の成形法により、フィルム、シート、射出成形体等に成形することができる。 The polyester resin of the present invention can be formed into a film, a sheet, an injection-molded body or the like by a known molding method.
　以下に実施例を示して本発明を具体的に説明するが、本発明は実施例に限定されるものではない。なお、実施例に記載された各測定値は次の方法によって測定したものである。 Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the examples. In addition, each measured value described in the Example is measured by the following method.
（１）還元粘度（ηｓｐ／ｃ）
　試料０．１ｇをパラクロロフェノール／テトラクロロエタン＝６／４（質量比）混合溶媒２５ｍｌに溶解し、ウベローデ粘度管を用いて３０℃で測定した。 (1) Reduced viscosity (ηsp / c)
0.1 g of a sample was dissolved in 25 ml of a mixed solvent of parachlorophenol / tetrachloroethane = 6/4 (mass ratio) and measured at 30 ° C. using an Ubbelohde viscosity tube.
（２）ＴＯＤΔ還元粘度
　まず、１．０ｇのポリエステル樹脂を２枚のテフロン（登録商標）シートの間に挟み、さらにそれを２枚のステンレス板に挟んでヒートプレス機に設置し、空気下、ポリエステル樹脂の融点＋３０℃の温度で２分間溶融後、１００ｋｇｆ／ｃｍ２の荷重をかけ、１分後に水につけて急冷してシートサンプルを作製した。
　このようにして熱履歴を与えたポリエステル樹脂試料を凍結粉砕して、１００メッシュ以下の粉末とし、７０℃で１２時間、１Ｔｏｒｒ以下で真空乾燥した。これを０．３ｇ秤量し、ガラス試験管に入れ、空気下で、１８０℃、６０分間加熱処理し、上記と同様の方法で還元粘度を測定し、以下の式からＴＯＤΔ還元粘度を算出した。
（ＴＯＤΔ還元粘度）＝（熱酸化試験前の還元粘度）－（熱酸化試験後の還元粘度） (2) TODΔ Reduced Viscosity First, 1.0 g of a polyester resin is sandwiched between two Teflon (registered trademark) sheets, and is further sandwiched between two stainless steel plates and installed in a heat press machine. After melting for 2 minutes at a temperature of the melting point of the polyester resin + 30 ° C., a load of 100 kgf / cm 2 was applied, and after 1 minute, it was immersed in water and rapidly cooled to prepare a sheet sample.
The polyester resin sample thus provided with a thermal history was freeze-pulverized to a powder of 100 mesh or less and vacuum-dried at 70 ° C. for 12 hours and 1 Torr or less. 0.3 g of this was weighed, placed in a glass test tube, heat-treated at 180 ° C. for 60 minutes in air, the reduced viscosity was measured by the same method as above, and the TODΔ reduced viscosity was calculated from the following equation.
(TODΔ reduced viscosity) = (reduced viscosity before thermal oxidation test) − (reduced viscosity after thermal oxidation test)
（３）融点
　ポリエステル樹脂５．０ｍｇをＤＳＣ用のアルミパンに入れ、３００℃まで加熱溶融した後、液体窒素で急冷した。そのように前処理したポリエステル樹脂を、（株）日立ハイテクサイエンス製の示差走査熱量分析計「Ｘ－ＤＳＣ７０００」を用いて測定した。２０℃から３００℃まで２０℃／分で昇温して得られたサーモグラム曲線からの吸熱ピークを融点とした。 (3) Melting point 5.0 mg of polyester resin was put into an aluminum pan for DSC, heated and melted to 300 ° C., and then rapidly cooled with liquid nitrogen. The polyester resin thus pretreated was measured using a differential scanning calorimeter “X-DSC7000” manufactured by Hitachi High-Tech Science Co., Ltd. The endothermic peak from the thermogram curve obtained by raising the temperature from 20 ° C. to 300 ° C. at 20 ° C./min was defined as the melting point.
（４）ポリエステル樹脂組成
　ポリエステル樹脂の組成及び組成比の決定は、共鳴周波数４００ＭＨｚの１Ｈ－ＮＭＲ測定（プロトン型核磁気共鳴分光測定）にて行った。測定装置はＶＡＲＩＡＮ社製、ＮＭＲ装置・４００－ＭＲを用い、溶媒には重クロロホルム／トリフルオロ酢酸＝８５／１５（質量比）を用いた。 (4) Polyester resin composition The composition and composition ratio of the polyester resin were determined by 1 H-NMR measurement (proton nuclear magnetic resonance spectroscopy) at a resonance frequency of 400 MHz. The measuring apparatus used was an NMR apparatus 400-MR manufactured by VARIAN, and deuterated chloroform / trifluoroacetic acid = 85/15 (mass ratio) was used as the solvent.
（５）ポリエステル樹脂試料中の全金属元素の含有量（ｐｐｍ）
　リンは蛍光Ｘ線法により求めた。その他の金属は、ポリマーを灰化／酸溶解後、高周波プラズマ発光分析及び原子吸光分析により求めた。いずれも予め作成した検量線から、試料中の元素の量を定量した。 (5) Content of all metal elements in polyester resin sample (ppm)
Phosphorus was determined by the fluorescent X-ray method. Other metals were determined by high-frequency plasma emission analysis and atomic absorption analysis after ashing / dissolving the polymer. In either case, the amount of element in the sample was quantified from a calibration curve prepared in advance.
（重縮合触媒溶液の調製）
（Ｉｒｇａｎｏｘ１２２２のエチレングリコール溶液の調製）
　窒素導入管、冷却管を備えたフラスコに、常温常圧下、エチレングリコール２．０リットルを加えた後、窒素雰囲気下２００ｒｐｍで攪拌しながら、リン化合物としてＩｒｇａｎｏｘ１２２２（ＢＡＳＦ社製）の２００ｇを加えた。さらに２．０リットルのエチレングリコールを追加した後、ジャケット温度の設定を１９６℃に変更して昇温し、内温が１８５℃以上になった時点から６０分間還流下で攪拌した。その後加熱を止め、直ちに溶液を熱源から取り去り、窒素雰囲気下を保ったまま、３０分以内に１２０℃以下まで冷却した。 (Preparation of polycondensation catalyst solution)
(Preparation of Irganox 1222 in ethylene glycol)
After adding 2.0 liters of ethylene glycol to a flask equipped with a nitrogen introduction tube and a cooling tube at room temperature and normal pressure, 200 g of Irganox 1222 (manufactured by BASF) was added as a phosphorus compound while stirring at 200 rpm in a nitrogen atmosphere. . Further, 2.0 liters of ethylene glycol was added, the temperature was raised by changing the jacket temperature setting to 196 ° C., and the mixture was stirred under reflux for 60 minutes from the time when the internal temperature reached 185 ° C. or higher. Thereafter, the heating was stopped, the solution was immediately removed from the heat source, and the solution was cooled to 120 ° C. or less within 30 minutes while maintaining the nitrogen atmosphere.
（アルミニウム化合物の水溶液の調製）
　冷却管を備えたフラスコに、常温常圧下、純水５．０リットルを加えた後、２００ｒｐｍで攪拌しながら、塩基性酢酸アルミニウム２００ｇを純水とのスラリーとして加えた。さらに全体として１０．０リットルとなるよう純水を追加して常温常圧で１２時間攪拌した。その後、ジャケット温度の設定を１００．５℃に変更して昇温し、内温が９５℃以上になった時点から３時間還流下で攪拌した。攪拌を止め、室温まで放冷し水溶液を得た。 (Preparation of aqueous solution of aluminum compound)
After adding 5.0 liters of pure water to a flask equipped with a cooling tube at room temperature and normal pressure, 200 g of basic aluminum acetate was added as a slurry with pure water while stirring at 200 rpm. Further, pure water was added so as to be 10.0 liters as a whole, and the mixture was stirred at room temperature and normal pressure for 12 hours. Thereafter, the jacket temperature was changed to 100.5 ° C., the temperature was raised, and the mixture was stirred under reflux for 3 hours from the time when the internal temperature reached 95 ° C. or higher. Stirring was stopped and the mixture was allowed to cool to room temperature to obtain an aqueous solution.
（アルミニウム化合物のエチレングリコール混合溶液の調製）
　上記方法で得たアルミニウム化合物水溶液に等容量のエチレングリコールを加え、室温で３０分間攪拌した後、内温８０～９０℃にコントロールし、徐々に減圧して、到達２７ｈＰａとして、数時間攪拌しながら系から水を留去し、２０ｇ／ｌのアルミニウム化合物のエチレングリコール溶液を得た。 (Preparation of ethylene glycol mixed solution of aluminum compound)
An equal volume of ethylene glycol was added to the aqueous aluminum compound solution obtained by the above method, and the mixture was stirred at room temperature for 30 minutes, then controlled to an internal temperature of 80 to 90 ° C., gradually reduced in pressure to reach 27 hPa, with stirring for several hours. Water was distilled off from the system to obtain an ethylene glycol solution of an aluminum compound at 20 g / l.
（アンチモン化合物のエチレングリコール溶液の調整）
　三酸化アンチモンをエチレングリコール溶液に溶解し、１４ｇ／ｌの三酸化アンチモンのエチレングリコール溶液を得た。 (Preparation of ethylene glycol solution of antimony compound)
Antimony trioxide was dissolved in an ethylene glycol solution to obtain an ethylene glycol solution of 14 g / l antimony trioxide.
（ゲルマニウム化合物の水溶液の調製）
　二酸化ゲルマニウムを水に溶解し、８ｇ／Ｌの二酸化ゲルマニウムの水溶液を得た。 (Preparation of aqueous solution of germanium compound)
Germanium dioxide was dissolved in water to obtain an aqueous solution of 8 g / L germanium dioxide.
（ＴＭＰＡのエチレングリコール溶液の調製）
　トリメチルリン酸（ＴＭＰＡ）をエチレングリコール溶液に溶解し、２０ｇ／ｌのＴＭＰＡのエチレングリコール溶液を得た。 (Preparation of TMPA ethylene glycol solution)
Trimethyl phosphoric acid (TMPA) was dissolved in an ethylene glycol solution to obtain a 20 g / l TMPA ethylene glycol solution.
（ＴＢＴの１－ブタノール溶液の調製）
　テトラ－ｎ－ブトキシチタン（ＴＢＴ）を１－ブタノールに溶解し、６８ｇ／ｌのＴＢＴの１－ブタノール溶液を得た。 (Preparation of 1-butanol solution of TBT)
Tetra-n-butoxytitanium (TBT) was dissolved in 1-butanol to obtain a 1-butanol solution of 68 g / l TBT.
（酢酸コバルトのエチレングリコール溶液の調製）
　酢酸コバルトをエチレングリコールに溶解し、２０ｇ／ｌの酢酸コバルトのエチレングリコール溶液を得た。 (Preparation of ethylene glycol solution of cobalt acetate)
Cobalt acetate was dissolved in ethylene glycol to obtain 20 g / l of an ethylene glycol solution of cobalt acetate.
実施例１
　攪拌機付き容量２リッターのステンレス製オートクレーブに２，５‐フランジカルボン酸４２８．５ｇ（２．７モル）、エチレングリコール２１９．５ｇ（３．５モル）を仕込み、２２０℃まで昇温しつつ、０．２５ＭＰａの加圧下で１５０分間エステル化反応を行い、オリゴマー混合物を得た。その後、調製したＩｒｇａｎｏｘ１２２２のエチレングリコール溶液、アルミニウム化合物のエチレングリコール混合溶液を所定の残存量になるように添加し、６０分間かけて２５０℃まで昇温しつつ、反応系の圧力を徐々に下げて、１３．３Ｐａ（０．１Ｔｏｒｒ）として、さらに２５０℃、１３．３Ｐａ下でポリエステル重縮合反応を６０分間行った。放圧に続き、微加圧下のレジンを冷水にストランド状に吐出して急冷し、その後２０秒間冷水中で保持した後、カッティングして長さ約３ｍｍ、直径約２ｍｍのシリンダー形状のペレットを得た。このポリエステルペレットの特性を表に示す。 Example 1
A 2-liter stainless steel autoclave equipped with a stirrer was charged with 428.5 g (2.7 mol) of 2,5-furandicarboxylic acid and 219.5 g (3.5 mol) of ethylene glycol. An esterification reaction was performed for 150 minutes under a pressure of 25 MPa to obtain an oligomer mixture. Thereafter, the prepared ethylene glycol solution of Irganox 1222 and the ethylene glycol mixed solution of aluminum compound are added so as to have a predetermined residual amount, and the temperature of the reaction system is gradually lowered while raising the temperature to 250 ° C. over 60 minutes. The polyester polycondensation reaction was further performed for 60 minutes at 250 ° C. and 13.3 Pa at 13.3 Pa (0.1 Torr). After releasing the pressure, the resin under slight pressure is discharged into cold water in a strand form and rapidly cooled, then held in cold water for 20 seconds, and then cut to obtain a cylinder-shaped pellet having a length of about 3 mm and a diameter of about 2 mm. It was. The characteristics of this polyester pellet are shown in the table.
実施例２～４
　実施例１の重合方法に準じて、但し、原料の種類と配合比率を変更して、ポリエステル樹脂実施例２～４を製造した。得られた樹脂の組成、残存金属量、物性は表に示した。これらは本願発明で規定した範囲を満たしており、良好な熱酸化安定性を示した。 Examples 2-4
According to the polymerization method of Example 1, polyester resins Examples 2 to 4 were produced by changing the kinds of raw materials and the mixing ratio. The composition, amount of residual metal, and physical properties of the obtained resin are shown in the table. These satisfied the range defined in the present invention and showed good thermal oxidation stability.
比較例１～６
　実施例１の重合方法に準じて、但し、原料の種類と配合比率を変更して、ポリエステル樹脂比較例１～５を製造した。得られた樹脂の組成、残存金属量、物性は表に示した。比較例１はリン化合物配合量が多すぎるため、比較例２～５は残存金属量が多すぎるため、熱酸化安定性がそれぞれ悪くＴＯＤΔ還元粘度が０．０３０ｄｌ／ｇ超であり、屋外用途としては適さない樹脂であることが分かる。また比較例６は、残存金属量は少ないが、融点の高さゆえ熱酸化試験前に行う熱処理温度が高いためにカルボキシル基が多く生成し、ＴＯＤΔ還元粘度が０．０３０ｄｌ／ｇ超となった。 Comparative Examples 1-6
According to the polymerization method of Example 1, polyester resin comparative examples 1 to 5 were produced by changing the kind of raw materials and the blending ratio. The composition, amount of residual metal, and physical properties of the obtained resin are shown in the table. Since Comparative Example 1 contains too much phosphorus compound, Comparative Examples 2 to 5 have too much residual metal, so the thermal oxidation stability is poor and the TODΔ reduced viscosity is more than 0.030 dl / g. It can be seen that is an unsuitable resin. In Comparative Example 6, although the amount of residual metal is small, the heat treatment temperature performed before the thermal oxidation test is high due to the high melting point, so that a large amount of carboxyl groups are generated, and the TODΔ reduced viscosity exceeds 0.030 dl / g. .
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　本発明のポリエステル樹脂は、長期熱安定性に優れる。よって、屋外で使用される太陽電池用途等の構成部材として有用であり、産業上の利用価値は大きい。 The polyester resin of the present invention is excellent in long-term thermal stability. Therefore, it is useful as a component for solar cell applications used outdoors and has a great industrial utility value.

Claims (6)

  1. 　ジカルボン酸成分とグリコール成分からなるポリエステル樹脂であって、ジカルボン酸成分としてフランジカルボン酸を１０モル％以上含み、下記要件（１）～（３）を満たすポリエステル樹脂。
    （１）全金属元素含有量がポリエステル樹脂の質量に対して１５０ｐｐｍ以下であること
    （２）リン元素含有量がポリエステル樹脂の質量に対して１００ｐｐｍ以下であること
    （３）下記式で表されるＴＯＤΔ還元粘度が０．０３０ｄｌ／ｇ以下であること
    （ＴＯＤΔ還元粘度）＝（熱酸化試験前の還元粘度）－（熱酸化試験後の還元粘度）
    （ここで、熱酸化試験とは、空気下、ポリエステル樹脂の融点＋３０℃の温度で２分間溶融後、同温度で１分間、荷重（１００ｋｇｆ／ｃｍ２）下に置く熱履歴を与えたポリエステル樹脂試料を、空気下、１８０℃の温度で６０分間加熱処理する試験である。）     A polyester resin comprising a dicarboxylic acid component and a glycol component, comprising 10 mol% or more of furandicarboxylic acid as a dicarboxylic acid component and satisfying the following requirements (1) to (3):
    (1) The total metal element content is 150 ppm or less with respect to the mass of the polyester resin. (2) The phosphorus element content is 100 ppm or less with respect to the mass of the polyester resin. (3) TODΔreduced viscosity is 0.030 dl / g or less (TODΔreduced viscosity) = (reduced viscosity before thermal oxidation test) − (reduced viscosity after thermal oxidation test)
    (Here, the thermal oxidation test is a polyester resin that has been melted for 2 minutes at a temperature of the melting point of the polyester resin + 30 ° C. in air and then given a thermal history under the load (100 kgf / cm 2 ) for 1 minute at the same temperature) This is a test in which a sample is heat-treated at 180 ° C. for 60 minutes in air.)
  2. 　ポリエステル重合時の触媒が、アルミニウム化合物及びリン化合物である請求項１に記載のポリエステル樹脂。 The polyester resin according to claim 1, wherein the catalyst at the time of polyester polymerization is an aluminum compound and a phosphorus compound.
  3. 　融点が２２０℃以下である請求項１～２のいずれかに記載のポリエステル樹脂。 3. The polyester resin according to claim 1, having a melting point of 220 ° C. or lower.
  4. 　請求項１～３のいずれかに記載のポリエステル樹脂を用いたフィルム。 A film using the polyester resin according to any one of claims 1 to 3.
  5. 　請求項１～３のいずれかに記載のポリエステル樹脂を用いたシート。 A sheet using the polyester resin according to any one of claims 1 to 3.
  6. 　請求項１～３のいずれかに記載のポリエステル樹脂を用いた射出成形体。
          An injection molded article using the polyester resin according to any one of claims 1 to 3.
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017038092A1 (en) * 2015-09-02 2017-03-09 Toyobo Co., Ltd. Polyester film containing furandicarboxylate unit
CN108285529A (en) * 2018-01-29 2018-07-17 陕西科技大学 A kind of preparation method for the Biodegradable film for promoting plant growth
US10815334B2 (en) 2015-09-04 2020-10-27 Mitsubishi Chemical Corporation Polyester resin, production method for said polyester resin, and polyester resin composition
US10941244B2 (en) 2016-03-30 2021-03-09 Toyobo Co., Ltd. Polyester film
WO2021172215A1 (en) * 2020-02-28 2021-09-02 東洋紡株式会社 Method for producing polyester and polyester produced by said method
US11318662B2 (en) 2015-12-28 2022-05-03 Toyobo Co., Ltd. Layered polyester film
US11325362B2 (en) 2015-12-28 2022-05-10 Toyobo Co., Ltd. Layered polyester film
US11325363B2 (en) 2017-03-01 2022-05-10 Toyobo Co., Ltd. Laminate including polyester film having furandicarboxylate unit and heat-sealable resin layer, and packaging bag
US11511473B2 (en) 2017-03-01 2022-11-29 Toyobo Co., Ltd. Method for producing polyester film having furandicarboxylate unit
WO2023132368A1 (en) * 2022-01-06 2023-07-13 東洋紡株式会社 Copolyester resin

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023539603A (en) * 2020-08-27 2023-09-15 フラニックス・テクノロジーズ・ベーフェー Preparation of polyesters containing 2,5-furandicarboxylate units using germanium catalysts
CN116601206A (en) 2020-12-23 2023-08-15 福兰尼克斯科技公司 Process for producing polyesters comprising 2, 5-furandicarboxylate units

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06100680A (en) 1992-09-22 1994-04-12 Kuraray Co Ltd Production of polyester
JPH0873719A (en) 1994-09-01 1996-03-19 Teijin Ltd Thermoplastic resin composition
JPH09227767A (en) 1996-02-21 1997-09-02 Teijin Ltd Polyester resin composition
JP2008291243A (en) * 2007-04-24 2008-12-04 Mitsubishi Chemicals Corp Thermoplastic resin including furan structure
JP2010254827A (en) * 2009-04-27 2010-11-11 National Institute Of Advanced Industrial Science & Technology High-molecular weight aliphatic polyester ether using biobase raw material and method for producing the same
JP2010280767A (en) * 2009-06-02 2010-12-16 Canon Inc Polyester resin, method for producing the same and molded article
JP2011132506A (en) * 2009-11-27 2011-07-07 Canon Inc Flame-retardant resin composition and molded article thereof

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6063465A (en) * 1998-04-23 2000-05-16 Hna Holdings, Inc. Polyester container and method for making same
JP5371259B2 (en) * 2008-02-20 2013-12-18 キヤノン株式会社 POLYESTER RESIN, PROCESS FOR PRODUCING THE SAME, COMPOSITION FOR MOLDED ARTICLE AND MOLDED ARTICLE
IT1387503B (en) * 2008-05-08 2011-04-13 Novamont Spa ALYPATIC-AROMATIC BIODEGRADABLE POLYESTER
US20100069553A1 (en) * 2008-09-18 2010-03-18 Eastman Chemical Company Polyester melt-phase compositions having improved thermo-oxidative stability, and methods of making and using them
JP5243997B2 (en) 2009-03-06 2013-07-24 東洋紡株式会社 Polyester film for solar cell and method for producing the same
JP2010260903A (en) * 2009-04-30 2010-11-18 Toyobo Co Ltd Polyester film
JP2011026470A (en) 2009-07-27 2011-02-10 Teijin Ltd Aromatic polyester, method for producing the same and aromatic polyester film
CN102050941B (en) 2009-11-03 2013-12-11 东丽纤维研究所（中国）有限公司 Macromolecular polymer and production method thereof
IT1400121B1 (en) * 2010-05-24 2013-05-17 Novamont Spa ALIPHATIC-AROMATIC COPOLIESTERE AND ITS BLENDS.
CN101899145B (en) 2010-07-28 2012-07-11 江南大学 Preparation method of 2, 5-furan diformyl polyester
US20130267674A1 (en) 2010-11-16 2013-10-10 Toshiyuki Kita Polyester resin
KR101309375B1 (en) * 2011-09-29 2013-09-17 롯데케미칼 주식회사 Polyester resin composition using biomass extract and method for preparing the same
US10800878B2 (en) 2011-10-14 2020-10-13 Eastman Chemical Company Polyester compositions containing furandicarboxylic acid or an ester thereof, cyclobutanediol and ethylene glycol
JP2013166874A (en) * 2012-02-16 2013-08-29 Toyobo Co Ltd Copolymerized polyester resin, and coating, coating agent, and adhesive using the same

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06100680A (en) 1992-09-22 1994-04-12 Kuraray Co Ltd Production of polyester
JPH0873719A (en) 1994-09-01 1996-03-19 Teijin Ltd Thermoplastic resin composition
JPH09227767A (en) 1996-02-21 1997-09-02 Teijin Ltd Polyester resin composition
JP2008291243A (en) * 2007-04-24 2008-12-04 Mitsubishi Chemicals Corp Thermoplastic resin including furan structure
JP2008291244A (en) * 2007-04-24 2008-12-04 Mitsubishi Chemicals Corp Method for producing polyester resin including furan structure
JP2010254827A (en) * 2009-04-27 2010-11-11 National Institute Of Advanced Industrial Science & Technology High-molecular weight aliphatic polyester ether using biobase raw material and method for producing the same
JP2010280767A (en) * 2009-06-02 2010-12-16 Canon Inc Polyester resin, method for producing the same and molded article
JP2011132506A (en) * 2009-11-27 2011-07-07 Canon Inc Flame-retardant resin composition and molded article thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3085723A4

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10407555B2 (en) 2015-09-02 2019-09-10 Toyobo Co., Ltd. Polyester film containing furandicarboxylate unit
WO2017038092A1 (en) * 2015-09-02 2017-03-09 Toyobo Co., Ltd. Polyester film containing furandicarboxylate unit
US10815334B2 (en) 2015-09-04 2020-10-27 Mitsubishi Chemical Corporation Polyester resin, production method for said polyester resin, and polyester resin composition
US11325362B2 (en) 2015-12-28 2022-05-10 Toyobo Co., Ltd. Layered polyester film
US11318662B2 (en) 2015-12-28 2022-05-03 Toyobo Co., Ltd. Layered polyester film
US10941244B2 (en) 2016-03-30 2021-03-09 Toyobo Co., Ltd. Polyester film
US11312830B2 (en) 2016-03-30 2022-04-26 Toyobo Co., Ltd. Polyester film
US11511473B2 (en) 2017-03-01 2022-11-29 Toyobo Co., Ltd. Method for producing polyester film having furandicarboxylate unit
US11325363B2 (en) 2017-03-01 2022-05-10 Toyobo Co., Ltd. Laminate including polyester film having furandicarboxylate unit and heat-sealable resin layer, and packaging bag
CN108285529B (en) * 2018-01-29 2020-05-12 陕西科技大学 Preparation method of biodegradable film capable of promoting plant growth
CN108285529A (en) * 2018-01-29 2018-07-17 陕西科技大学 A kind of preparation method for the Biodegradable film for promoting plant growth
WO2021172215A1 (en) * 2020-02-28 2021-09-02 東洋紡株式会社 Method for producing polyester and polyester produced by said method
WO2023132368A1 (en) * 2022-01-06 2023-07-13 東洋紡株式会社 Copolyester resin

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